U.S. patent application number 13/807210 was filed with the patent office on 2013-08-22 for photosensitive resin composition, photosensitive resin composition film, and semiconductor device using the photosensitive resin composition or photosensitive resin composition film.
This patent application is currently assigned to Toray Industries, Inc.. The applicant listed for this patent is Hiroyuki Niwa. Invention is credited to Hiroyuki Niwa.
Application Number | 20130214379 13/807210 |
Document ID | / |
Family ID | 45401864 |
Filed Date | 2013-08-22 |
United States Patent
Application |
20130214379 |
Kind Code |
A1 |
Niwa; Hiroyuki |
August 22, 2013 |
PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN COMPOSITION
FILM, AND SEMICONDUCTOR DEVICE USING THE PHOTOSENSITIVE RESIN
COMPOSITION OR PHOTOSENSITIVE RESIN COMPOSITION FILM
Abstract
A photosensitive resin composition contains: (a) an
alkali-soluble polyimide; (b) a compound which has two or more
epoxy groups and/or oxetanyl groups in each molecule; and (c) a
quinonediazide compound. Less than 10 parts by weight of an acrylic
resin is contained per 100 parts by weight of the polyimide (a);
and the content of the compound (b) is not less than 20 parts by
weight per 100 parts by weight of the polyimide (a).
Inventors: |
Niwa; Hiroyuki; (Otsu-shi,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Niwa; Hiroyuki |
Otsu-shi |
|
JP |
|
|
Assignee: |
Toray Industries, Inc.
Tokyo
JP
|
Family ID: |
45401864 |
Appl. No.: |
13/807210 |
Filed: |
June 10, 2011 |
PCT Filed: |
June 10, 2011 |
PCT NO: |
PCT/JP2011/063339 |
371 Date: |
February 25, 2013 |
Current U.S.
Class: |
257/499 ;
156/272.2; 156/306.6; 430/280.1 |
Current CPC
Class: |
G03F 7/0236 20130101;
H01L 24/92 20130101; H01L 2924/12043 20130101; H01L 24/81 20130101;
H01L 2224/27416 20130101; H01L 2224/13147 20130101; H01L 2224/2919
20130101; H01L 2224/83856 20130101; H01L 2224/29036 20130101; H01L
2924/15788 20130101; H01L 24/83 20130101; H01L 2924/10253 20130101;
H01L 2224/11845 20130101; H01L 2224/81203 20130101; H01L 2224/81903
20130101; H01L 24/32 20130101; H01L 2224/83862 20130101; H01L
2224/1146 20130101; G03F 7/0226 20130101; H01L 2224/276 20130101;
H01L 2224/73204 20130101; H01L 2224/9211 20130101; H01L 23/293
20130101; H01L 2224/83191 20130101; H01L 24/27 20130101; H01L
2924/15787 20130101; H01L 2924/351 20130101; H01L 2924/1461
20130101; H01L 24/11 20130101; H01L 24/16 20130101; H01L 24/26
20130101; H01L 2224/83101 20130101; C08L 79/08 20130101; H01L 24/29
20130101; H01L 2224/32225 20130101; C08G 73/1046 20130101; H01L
2224/73104 20130101; H01L 2224/82203 20130101; H01L 24/13 20130101;
C08G 73/1042 20130101; G03F 7/0233 20130101; G03F 7/038 20130101;
C08G 73/106 20130101; H01L 2224/1148 20130101; C08L 79/08 20130101;
C08L 63/00 20130101; C08L 79/08 20130101; C08L 33/04 20130101; C08L
63/00 20130101; H01L 2224/83101 20130101; H01L 2924/00014 20130101;
H01L 2224/1146 20130101; H01L 2924/00014 20130101; H01L 2224/11845
20130101; H01L 2924/00014 20130101; H01L 2224/13147 20130101; H01L
2924/00014 20130101; H01L 2224/81203 20130101; H01L 2924/00014
20130101; H01L 2224/82203 20130101; H01L 2924/00014 20130101; H01L
2224/83862 20130101; H01L 2924/00014 20130101; H01L 2224/276
20130101; H01L 2924/00014 20130101; H01L 2224/2919 20130101; H01L
2924/0665 20130101; H01L 2224/9211 20130101; H01L 2224/81 20130101;
H01L 2224/83 20130101; H01L 2924/10253 20130101; H01L 2924/00
20130101; H01L 2924/1461 20130101; H01L 2924/00 20130101; H01L
2924/351 20130101; H01L 2924/00 20130101; H01L 2924/15787 20130101;
H01L 2924/00 20130101; H01L 2924/15788 20130101; H01L 2924/00
20130101; H01L 2924/12043 20130101; H01L 2924/00 20130101 |
Class at
Publication: |
257/499 ;
430/280.1; 156/272.2; 156/306.6 |
International
Class: |
G03F 7/023 20060101
G03F007/023; H01L 23/00 20060101 H01L023/00; H01L 23/29 20060101
H01L023/29 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 2, 2010 |
JP |
2010-151596 |
Claims
1. A photosensitive resin composition comprising: (a) an
alkali-soluble polyimide which has a structural unit represented by
general formula (1), while having a structure represented by
general formula (2) and/or (3) at at least one end of the main
chain; (b) a compound which has two or more epoxy groups and/or
oxetanyl groups in each molecule; and (c) a quinonediazide
compound, wherein the content of the compound (b) is not less than
20 parts by weight per 100 parts by weight of the polyimide (a),
##STR00013## wherein X represents a monovalent organic group having
at least one selected from the group consisting of a carboxyl
group, a phenolic hydroxyl group, a sulfonic acid group and a thiol
group, and Y represents a divalent organic group having at least
one selected from the group consisting of a carboxyl group, a
phenolic hydroxyl group, a sulfonic acid group and a thiol group;
and wherein R.sup.1 represents a tetra- to tetradeca-valent organic
group, R.sup.2 represents a di- to dodeca-valent organic group, and
R.sup.3 and R.sup.4 each independently represents at least one
group selected from the group consisting of a carboxyl group, a
phenolic hydroxyl group, a sulfonic acid group and a thiol group,
.alpha. and .beta. each independently represents an integer of 0 to
10.
2. The photosensitive resin composition according to claim 1,
wherein the compound (b) is a compound having two or more epoxy
groups.
3. The photosensitive resin composition according to claim 1 or 2,
wherein the imidization ratio of the polyimide (a) is not less than
90%.
4. The photosensitive resin composition according to claim 1,
wherein the content of the compound (b) is not less than 40 parts
by weight per 100 parts by weight of the polyimide (a).
5. The photosensitive resin composition according to claim 1,
wherein the content of an acrylic resin contained is less than 10
parts by weight per 100 parts by weight of the polyimide (a).
6. A photosensitive resin composition film comprising: (a) an
alkali-soluble polyimide which has a structural unit represented by
general formula (1), while having a structure represented by
general formula (2) and/or (3) at at least one end of the main
chain; (b) a compound which has two or more epoxy groups and/or
oxetanyl groups in each molecule; and (c) a quinonediazide
compound, wherein the content of the compound (b) is not less than
20 parts by weight per 100 parts by weight of the polyimide (a),
##STR00014## wherein X represents a monovalent organic group having
at least one selected from the group consisting of a carboxyl
group, a phenolic hydroxyl group, a sulfonic acid group and a thiol
group, and Y represents a divalent organic group having at least
one selected from the group consisting of a carboxyl group, a
phenolic hydroxyl group, a sulfonic acid group and a thiol group;
and wherein R.sup.1 represents a tetra- to tetradeca-valent organic
group, R.sup.2 represents a di- to dodeca-valent organic group, and
R.sup.3 and R.sup.4 each independently represents at least one
group selected from the group consisting of a carboxyl group, a
phenolic hydroxyl group, a sulfonic acid group and a thiol group,
.alpha. and .beta. each independently represents an integer of 0 to
10.
7. The photosensitive resin composition film according to claim 6,
wherein the compound (b) has two or more epoxy groups in each
molecule.
8. The photosensitive resin composition film according to claim 6
or 7, wherein the content of the compound (b) is not less than 40
parts by weight per 100 parts by weight of the polyimide (a).
9. The photosensitive resin composition film according to claim 6,
wherein the content of an acrylic resin contained is less than 10
parts by weight per 100 parts by weight of the polyimide (a).
10. A laminate comprising a support, the photosensitive resin
composition film according to claim 6, and a cover film in this
order.
11. A cured product of the photosensitive resin composition
according to claim 1 or of the photosensitive resin composition
film according to claim 6.
12. A semiconductor device comprising a cured product of the
photosensitive resin composition according to claim 1 or of the
photosensitive resin composition film according to claim 6.
13. A semiconductor device comprising a cured product of the
photosensitive resin composition according to claim 1 or of the
photosensitive resin composition film according to claim 6 between
circuit members, wherein the edge of the cured product is located
at the inner side as compared to the edge of a circuit member.
14. A semiconductor device obtained by interposing the
photosensitive resin composition according to claim 1 or the
photosensitive resin composition film according to claim 6 between
a first circuit member and a second circuit member, opening a
desired area by patterning, and then electrically connecting the
first circuit member and the second circuit member by heating and
compression, wherein the edge of the photosensitive resin
composition or the photosensitive resin composition film is located
at the inner side as compared to the edges of the first circuit
member and the second circuit member.
15. A method for producing a semiconductor device, wherein the
photosensitive resin composition according to claim 1 or the
photosensitive resin composition film according to claim 6 is
interposed between a first circuit member and a second circuit
member, and the first circuit member and the second circuit member
are electrically connected by heating and compression.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is the U.S. National Phase application of
PCT International Application No. PCT/JP2011/063339, filed Jun. 10,
2011, and claims priority to Japanese Patent Application No.
2010-151596, filed Jul. 2, 2010, the disclosures of each of these
applications are incorporated herein by reference in their
entireties for all purposes.
FIELD OF THE INVENTION
[0002] The present invention relates to a photosensitive resin
composition and a photosensitive resin composition film. More
particularly, the present invention relates to a photosensitive
composition that is used for a semiconductor element, a
semiconductor device having multilayer structure, a photosensitive
composition such as an image sensor and so on, particularly a
photosensitive resin composition having an adhesion function.
BACKGROUND OF THE INVENTION
[0003] In recent years, various forms of packages have been
proposed for achieving improvement of performance of a
semiconductor device and electronic components, and cost reduction.
For example, a method is known in which the periphery of an element
is surrounded by a resin spacer having adhesion, and a substrate
such as glass is attached to the upper surface to form a hollow
structure for forming a hollow package such as an image sensor or
an HEMS (see, for example, Patent Document 1). In such an
application, an adhesive, which allows patterning by
photolithography, is required.
[0004] As the size is reduced, the operation speed is increased and
the density of wiring is increased particularly in semiconductor
devices such as memories and system LSIs, studies are constantly
conducted on practical applications of a semiconductor package of
three-dimensional structure in which silicon chips are each
provided on both the front and rear surfaces with an electrode
structure such as a pad and a bump by a through via, rather than
connection by conventional wire bonding, and laminated together to
secure conduction between chips (see Non-patent Document 1). In a
package having such a structure, the use of an adhesive for
laminating the chips is contemplated. The adhesive used here
preferably has such a photosensitivity that an adhesive on an
electrode can be removed by patterning for exposing an electrode
part to secure conduction between chips, in addition to properties
prerequisite for assembly reliability such as a low stress
property, adhesion, an insulating property and such a heat
resistance that reflow soldering can be endured.
[0005] Materials using a polyimide precursor are known as adhesives
having a photosensitivity and a high heat resistance (see, for
example, Patent Document 2), but these materials are required to be
heat-cured at a high temperature of 300.degree. C. or higher for a
ring-closure reaction to form the polyimide. Thus, there is a
concern that thermal stress associated with cure shrinkage is so
large that the substrate is warped and the adhesion strength is
reduced. For solving these problems, there has been proposed a
negative tone photosensitive material, the curing temperature of
which is reduced by using an alkali-soluble polyimide as a base
resin (see, for example, Patent Document 3). A positive tone
photosensitive material, which can be cured at a low temperature
similarly by using an alkali-soluble polyimide as a base resin, is
also known (see, for example, Patent Documents 4 and 5).
PATENT DOCUMENTS
[0006] Patent Document 1: Japanese Patent Laid-open Publication No.
2008-286877 [0007] Patent Document 2: Japanese Patent Laid-open
Publication No. 04-337380 [0008] Patent Document 3: Japanese Patent
Laid-open Publication No. 2008-281597 [0009] Patent Document 4:
Japanese Patent Laid-open Publication No. 2006-313237 [0010] Patent
Document 5: Japanese Patent Laid-open Publication No.
2009-20246
NON-PATENT DOCUMENT
[0010] [0011] Non-patent Document 1: Seiichi Denda, "TSV Technique
for Three-dimensional Mounting" (2009)
SUMMARY OF THE INVENTION
[0012] In the resin design described in Patent Document 3, an
alkali-soluble polyimide has high thermal stress, and exhibits an
insufficient thermocompression property to a support substrate such
as a silicon wafer or a glass substrate in some cases. Further, the
material is a negative tone photosensitive material, and the
pattern shape tends to be an inverse tapered shape. Thus, there is
such a problem that defects such as collapse of a pattern occurs,
or it is difficult to form a sputtered film for the purpose of
formation of wiring on the side wall of the pattern. On the other
hand, the positive tone photosensitive materials described in
Patent Documents 4 and 5 do not have a sufficient adhesion
function, and are difficult to be formed into a B stage sheet and
used because a film after drying off a solvent is fragile.
[0013] The present invention provides a positive tone
photosensitive resin composition and photosensitive resin
composition film, each of which has small stress after curing and
exhibits excellent adhesion.
[0014] The present invention, according to one exemplary
embodiment, is a photosensitive resin composition containing: (a)
an alkali-soluble polyimide which has a structural unit represented
by general formula (1), while having a structure represented by
general formula (2) and/or (3) at at least one end of the main
chain; (b) a compound which has two or more epoxy groups and/or
oxetanyl groups in each molecule; and (c) a naphthoquinonediazide
compound, wherein the content of the compound (b) is not less than
20 parts by weight per 100 parts by weight of the polyimide
(a).
[0015] According to the present invention, there is obtained a
photosensitive resin composition and a photosensitive resin
composition film, each of which is capable of forming a positive
tone pattern by photolithography, has small stress after curing,
and exhibits a high strength of adhesion with a semiconductor
element and a support member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows a multilayer wiring substrate prepared using a
photosensitive resin composition of an embodiment of the present
invention.
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0017] A photosensitive resin composition of an embodiment of the
present invention contains (a) an alkali-soluble polyimide which
has a structural unit represented by general formula (1), while
having a structure represented by general formula (2) and/or (3) at
at least one end of the main chain; (b) a compound which has two or
more epoxy groups and/or oxetanyl groups in each molecule; and (c)
a naphthoquinonediazide compound, wherein the content of the
compound (b) is not less than 20 parts by weight per 100 parts by
weight of the polyimide (a).
[0018] The polyimide as component (a) is an alkali-soluble
polyimide. The term "alkali-soluble" used herein means that the
solubility in a 2.38% aqueous tetramethyl ammonium hydroxide
solution is not less than 0.1 g/100 mL. For exhibiting an
alkali-solubility and allowing good pattern processing, the
polyimide as component (a) has a structural unit represented by
general formula (1) below, while having a structure represented by
general formula (2) and/or (3) at at least one end of the main
chain.
##STR00001##
[0019] In the formula, X represents a monovalent organic group
having at least one selected from the group consisting of a
carboxyl group, a phenolic hydroxyl group, a sulfonic acid group
and a thiol group, and Y represents a divalent organic group having
at least one selected from the group consisting of a carboxyl
group, a phenolic hydroxyl group, a sulfonic acid group and a thiol
group. X is preferably an aromatic group, and Y is preferably an
aromatic group, or a group having a carbon-carbon double bond.
Particularly, X and Y preferably have a phenolic hydroxyl group or
a thiol group.
[0020] R.sup.1 represents a tetra- to tetradeca-valent organic
group, R.sup.2 represents a di- to dodeca-valent organic group, and
R.sup.3 and R.sup.4 each independently represent at least one group
selected from the group consisting of a carboxyl group, a phenolic
hydroxyl group, a sulfonic acid group and a thiol group. .alpha.
and .beta. each independently represent an integer of 0 to 10.
[0021] In general formula (1) above, R.sup.1 represents a
structural component derived from a tetracarboxylic dianhydride.
Particularly, it is preferably an organic group containing an
aromatic group or a cyclic aliphatic group and having 5 to 40
carbon atoms.
[0022] Specific examples of the tetracarboxylic dianhydride include
aromatic tetracarboxylic dianhydrides such as pyromellitic
dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride,
2,3,3',4'-biphenyltetracarboxylic dianhydride,
2,2',3,3'-biphenyltetracarboxylic dianhydride,
3,3',4,4'-benzophenonetetracarboxylic dianhydride,
2,2',3,3'-benzophenonetetracarboxylic dianhydride,
2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,
1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride,
bis(3,4-dicarboxyphenyl)methane dianhydride,
bis(2,3-dicarboxyphenyl)methane dianhydride,
bis(3,4-dicarboxyphenyl)sulfone dianhydride,
bis(3,4-dicarboxyphenyl)ether dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride,
9,9-bis(3,4-dicarboxyphenyl)fluorensic dianhydride,
9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorensic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride,
2,3,5,6-pyridinetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride and
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride,
aliphatic tetracarboxylic dianhydrides such as
butanetetracarboxylic dianhydride and
1,2,3,4-cyclopentanetetracarboxylic dianhydride, and acid
dianhydrides having a structure shown below. They are used alone or
in combination of two or more thereof.
##STR00002##
[0023] Here, R.sup.9 represents a group selected from an oxygen
atom, C(CF.sub.3).sub.2, C(CH.sub.3).sub.2, CO, COO and SO.sub.2,
and R.sup.10 and R.sup.11 each represent a group selected from a
hydrogen atom, a hydroxyl group and a thiol group.
[0024] In general formula (1) above, R.sup.2 represents a
structural component derived from a diamine. Particularly, it is
preferably an organic group containing an aromatic group or a
cycloaliphatic group and having 5 to 40 carbon atoms.
[0025] Specific examples of the diamine include
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl methane,
3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane,
3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene,
1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,
benzidine, m-phenylenediamine, p-phenylenediamine,
1,5-naphthalenediamine, 2,6-naphthalanediamine,
bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone,
bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether,
1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl,
2,2'-diethyl-4,4'-diaminobiphenyl,
3,3'-dimethyl-4,4'-diaminobiphenyl,
3,3'-diethyl-4,4'-diaminobiphenyl,
2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl,
3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl,
2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl,
9,9-bis(4-aminophenyl)fluorene or compounds with the aromatic ring
of the above-mentioned compound substituted with an alkyl group or
a halogen atom, aliphatic cyclohexyldiamine,
methylenebiscyclohexylamine, and diamines having a structure shown
below. They are used alone or in combination of two or more
thereof.
##STR00003##
[0026] Here, R.sup.9 represents a group selected from an oxygen
atom, C(CF.sub.3).sub.2, C(CH.sub.3).sub.2, CO, COO and SO.sub.2,
and R.sup.10 and R.sup.13 each represent a group selected from a
hydroxyl group and a thiol group.
[0027] Among them, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl
ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl methane,
3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane,
3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide,
4,4'-diaminodiphenyl sulfide, m-phenylenediamine,
p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene,
9,9-bis(4-aminophenyl)fluorene, diamines having a structure shown
below, and so on are preferable.
##STR00004##
[0028] R.sup.9 represents a group selected from an oxygen atom,
C(CF.sub.3).sub.2, C(CH.sub.3).sub.2, and SO.sub.2, and R.sup.10
and R.sup.13 each represent a group selected from a hydroxyl group
and a thiol group.
[0029] In general formula (1), R.sup.3 and R.sup.4 each
independently represent at least one selected from the group
consisting of a carboxyl group, a phenolic hydroxyl group, a
sulfonic acid group and a thiol group. By adjusting the amounts of
R.sup.3 and R.sup.4, the rate of dissolution of the polyimide in an
aqueous alkali solution is changed, so that a photosensitive resin
composition having an appropriate dissolution rate can be
obtained.
[0030] Further, for improving adhesion with a substrate, and so on,
an aliphatic group having a siloxane structure may be copolymerized
with R.sup.2 within the bounds of not reducing the heat resistance.
Specific examples of the diamine component include those obtained
by copolymerizing 1 to 10 mol % of bis(3-aminopropyl)tetramethyl
disiloxane, bis(p-amino-phenyl)octamethyl pentasiloxane and so
on.
[0031] General formulae (2) and (3) show the structure of the end
of a polyimide having a structural unit represented by general
formula (1). The polyimide have two ends, at least one of which
should have a structure represented by general formula (2) and/or
(3).
[0032] A polyimide having a structure represented by general
formula (2) and/or (3) at the end of the main chain can be
synthesized using a publicly known method with apart of a diamine
replaced by a monoamine which is an end capping agent, or with a
tetracarboxylic dianhydride replaced by a dicarboxylic anhydride
which is an end capping agent. A polyimide precursor is obtained
by, for example, a method in which a tetracarboxylic dianhydride, a
diamine compound and a monoamine are reacted at a low temperature,
a method in which a tetracarboxylic dianhydride, a dicarboxylic
anhydride and a diamine compound are reacted at a low temperature,
or a method in which a diester is obtained by a tetracarboxylic
dianhydride and an alcohol, and then reacted with a diamine and a
monoamine in the presence of a condensation agent. Thereafter, a
polyimide can be synthesized by imidizing the obtained polyimide
precursor by a publicly known imidization reaction.
[0033] In general formula (2), X is derived from a primary
monoamine which is an end capping agent. As the primary monoamine
used as an end capping agent, 5-amino-8-hydroxyquinoline,
1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene,
1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene,
2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,
2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene,
1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene,
2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene,
2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic
acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic
acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid,
3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid,
3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol,
4-aminophenol, 2-aminothiophenol, 3-aminothiophenol,
4-aminothiophenol and so on are preferable. They are used alone or
in combination of two or more thereof.
[0034] In general formula (3), Y is derived from a dicarboxylic
anhydride which is an end capping agent. As the acid anhydride used
as an end capping agent, 4-carboxyphthalic anhydride,
3-hydroxyphthalic anhydride, cis-aconitic anhydride and so on are
preferable. They are used alone or in combination of two or more
thereof.
[0035] The polyimide, which has a structural unit represented by
general formula (1), while having a structure represented by
general formula (2) and/or (3) at at least one of the ends of the
main chain, may be one having a repeating unit consisting of only
the structural unit represented by general formula (1), or may be a
copolymer with other structural units, or may include a precursor
of the structural unit represented by general formula (1) (polyamic
acid structure). At this time, the structural unit represented by
general formula (1) is preferably contained in an amount of no less
than 50 mol % of the total amount of the polyimide. The type and
the amount of a structural unit used for copolymerization or mixing
are preferably selected within the bounds of not deteriorating the
heat resistance of a polyimide obtained by a final heating
treatment.
[0036] The imidization ratio of the polyimide (a) can be easily
determined by the following method. Here, the imidization ratio
means a mole percentage of a polyimide precursor converted into a
polyimide in synthesis of a polyimide through a polyimide precursor
as described above. First, the infrared spectrum of a polyimide
precursor is measured, and the presence of absorption peaks (around
1780 cm.sup.-1 and around 1377 cm.sup.-1) originating from a
polyimide is confirmed. Next, the polyimide precursor is subjected
to a heat treatment at 350.degree. C. for an hour, the infrared
spectrum is then measured again, and peak intensities around 1377
cm.sup.-1 before and after the heat treatment are compared. The
imidization ratio of the polymer before the heat treatment is
determined with the imidization ratio of the polymer after the heat
treatment set to 100%. The imidization ratio of the polyimide (a)
is preferably not less than 90%.
[0037] The end capping agent introduced into the polyimide (a) can
be detected by the following method. For example, a polyimide, into
which an end capping agent is introduced, is dissolved in an acidic
solution to be decomposed into an amine component and a carboxylic
anhydride component that are constituent units of the polyimide,
and these components are analyzed by gas chromatography (GC) or
NMR. Alternatively, a polyimide, into which an end capping agent is
introduced, is directly analyzed using a pyrolysis gas
chromatograph (PGC) or an infrared spectrum and a .sup.13CNMR
spectrum.
[0038] It is desirable that the weight average molecular weight of
the polyimide (a) should be 10000 to 100000 inclusive. When two or
more types of polyimides are contained, the weight average
molecular weight of at least one thereof is preferably in the range
described above. If the weight average molecular weight is less
than 10000, the mechanical strength may significantly decrease,
leading to a reduction in adhesion strength. The weight average
molecular weight is preferably not less than 12000. On the other
hand, the weight average molecular weight is more than 100000, the
solubility in an alkali development liquid may decrease, leading to
occurrence of development residues. The weight average molecular
weight is preferably not more than 50000. The weight average
molecular weight in the present invention is measured by gel
permeation chromatography (GPC), and calculated in terms of
polystyrene.
[0039] The photosensitive resin composition of the present
invention preferably contains (b) a compound having two or more
epoxy groups and/or oxetanyl groups in each molecule, wherein the
compound (b) is a compound having two or more epoxy groups.
Examples of the compound having two or more epoxy groups in each
molecule include a bisphenol A-type epoxy compound, a bisphenol
F-type epoxy compound, a novolac-type epoxy compound, a
biphenol-type epoxy compound, a biphenyl-type epoxy compound, a
glycidyl amine-type epoxy compound and a cyclic aliphatic epoxy
compound. Specific examples include "jER (registered trademark)"
828, 834, 1001, 1002, 1003, 1004, 1005, 1007, 1010, 1100L, 630,
ESCN-220L, 220F, 220H, 220HH, 180H65, 1032H60, YX4000H, 152, 157S70
and 1031 (Mitsubishi Chemical Corporation), "Epolite" 40E, 100E,
200E, 400E, 70P, 200P, 400P, 1500NP, 80MF, 4000 and 3002
(manufactured by Kyoeisha Chemical Co., Ltd), "ADEKA RESIN
(registered trademark)" EP-4000S and EP-4003S (manufactured by
ADEKA Corporation), "Denacol" EX-212L, EX-214L, EX-216L, EX-850L
and EX-321L (manufactured by Nagase ChemteX Corporation), "EPICLON
(registered trademark)" 850, EXA-850CRP, 860 and EXA-4701
(manufactured by DIC Corporation), "TEPIC" S, G and P (manufactured
by Nissan Chemical Industries, Ltd.), and GAN, GOT, EPPN502H,
NC3000 and NC6000 (manufactured by Nippon Kayaku Co., Ltd.).
Specific examples of the compound having two or more oxetanyl
groups in each molecule include OXT-121, OXT-221, OX-SQ-H, OXT-191,
PNOX-1009 and RSOX (manufactured by Toagosei Co., Ltd.), and
"ETERNACOLL" OXBP and OXTP (manufactured by UBE INDUSTRIES,
LTD.).
[0040] For securing the adhesion strength and the fluidity during
thermocompression, and reducing stress of a cured film, the content
of the compound (b) should be not less than 20 parts by weight,
more preferably not less than 40 parts by weight, per 100 parts by
weight of the polyimide (a). The content of the compound (b) is
preferably not more than 100 parts by weight per 100 parts by
weight of the polyimide (a) from the viewpoint of the heat
resistance and development characteristic.
[0041] The photosensitive resin composition of the present
invention preferably contains a naphthoquinonediazide compound (c).
The naphthoquinonediazide compound used is not particularly
limited, but one example is a compound with a
naphthoquinonediazidesulfonic acid ester-bonded to a compound
having a phenolic hydroxyl group. As the compound having a phenolic
hydroxyl group, a compound having two or more phenol cores in each
molecule is preferably used. The naphthoquinonediazide compound can
be synthesized by a publicly known esterification reaction of a
compound having a phenolic hydroxyl group and a
naphthoquinonediazidesulfonic acid chloride.
[0042] Specific examples of the compound having a phenolic hydroxyl
group include the following compounds (all manufactured by Honshu
Chemical Industry Co., Ltd.).
##STR00005## ##STR00006## ##STR00007## ##STR00008##
[0043] Among these compounds having a phenolic hydroxyl group,
TekP-4HBPA, TrisP-HAP, TrisP-PA and Phcc-AP are preferably used
from the viewpoint of the sensitivity and resolution.
[0044] As the naphthoquinonediazidesulfonic acid chloride as a raw
material, 4-naphthoquinonediazidesulfonic acid chloride or
5-naphthoquinonediazidesulfonic acid chloride can be used. The
4-naphthoquinonediazidesulfonate compound has an absorption in an
i-line (wavelength: 365 nm) range, and is therefore suitable for
i-line exposure. The 5-naphthoquinonediazidesulfonate compound has
an absorption in a wide wavelength range, and is therefore suitable
for exposure in a wide wavelength range. It is preferable to select
the 4-naphthoquinonediazidesulfonate compound or the
5-naphthoquinonediazidesulfonate compound according to a wavelength
at which the compound is exposed. The
4-naphthoquinonediazidesulfonate compound and the
5-naphthoquinonediazidesulfonate compound can also be mixed and
used. There are preferably two or more
naphthoquinonediazidesulfonate structures from the viewpoint of the
resolution.
[0045] The added amount of the naphthoquinonediazide compound is
not particularly limited, but is preferably 5 to 40 parts by
weight, further preferably 10 to 30 parts by weight, per 100 parts
by weight of the polyimide (a). The added amount of the
naphthoquinonediazide compound is preferably not less than 5 parts
by weight for obtaining a still better dissolution contrast. On the
other hand, if the added amount of the naphthoquinonediazide
compound is more than 40 parts by weight, a film or a cured film
formed using a photosensitive resin composition may become
fragile.
[0046] The photosensitive resin composition of the present
invention may contain an acrylic resin. The acrylic resin used
herein is a polymer of an unsaturated carboxylic acid, an
unsaturated carboxylate or the like, which is the acrylic resin
described in Japanese Patent Laid-open Publication No. 2009-20246,
and so on. However, if the acrylic resin is contained in a large
amount, the heat stability is degraded at 250.degree. C. or higher,
so that the reliability is impaired. In addition, the film after
drying off a solvent becomes fragile, so that it is very difficult
to form the composition into a B stage film. In this respect, the
content of the acrylic resin is preferably less than 10 parts by
weight per 100 parts by weight of the polyimide (a), and preferably
substantially no acrylic resin is contained particularly when the
photosensitive resin composition of the present invention is used
as a film.
[0047] The photosensitive resin composition of the present
invention may contain a surfactant, inorganic particles such as
silicon dioxide and titanium dioxide, additives such as a
crosslinker, a crosslinking accelerator, a sensitizer, a
dissolution adjustor, a stabilizer and an anti-foaming agent, a
silane coupling agent, a titanium chelating agent, a zirconia
chelating agent and so on.
[0048] It is preferable to add an organic solvent to the
photosensitive resin composition of the present invention. The
organic solvent used should be one that is capable of dissolving or
dispersing the components.
[0049] Specific examples of the organic solvent include ethers such
as ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, propylene glycol monomethyl ether, propylene glycol
monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol
diethyl ether and ethylene glycol dibutyl ether; acetates such as
ethylene glycol monoethyl ether acetate, propylene glycol
monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl
acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
methyl lactate, ethyl lactate and butyl lactate; ketones such as
acetone, methyl ethyl ketone, acetylacetone, methyl propyl ketone,
methyl butyl ketone, methyl isobutyl ketone, cyclopentanone and
2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol,
pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol,
3-methyl-3-methoxybutanol and diacetone alcohol; aromatic
hydrocarbons such as toluene and xylene; and others such as
N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide and
.gamma.-butyrolactone.
[0050] The photosensitive resin composition may be filtered using a
filter paper or a filter. The method for filtration is not limited,
but mention is made of a method of filtering the composition by
filtration under pressure using a membrane filter with a retention
particle diameter of 0.2 .mu.m to 10 .mu.m.
[0051] For the photosensitive resin composition of the present
invention, the shape before curing is not limited, and mention is
made of, for example, a varnish shape and a film shape. The film
shape may be a shape of a sheet formed on a support. When the
composition is used in the varnish shape, a solution obtained by
dissolving in an organic solvent the components (a) to (c) and
components added as necessary can be used. A photosensitive resin
composition film is obtained by applying the photosensitive resin
composition of the present invention onto a support, and then
drying the applied composition as necessary.
[0052] A laminate of the present invention preferably has a
support, the photosensitive resin composition film of the present
invention and a cover film in this order. The photosensitive resin
composition film of the present invention is preferably formed on a
support. The support used in the laminate of the present invention
is not particularly limited, but various kinds of films that are
usually commercially available, such as a polyethylene
terephthalate (PET) film, a polyethylene film, a polypropylene (PP)
film, a polyphenylene sulfide film and a polyimide film, can be
used. The surface of the support may be treated with silicone, a
silane coupling agent, an aluminum chelating agent, polyurea and so
on for adjusting a wetting property, an adhesion property and a
release property with the photosensitive resin composition. The
thickness of the support is not particularly limited, but is
preferably in a range of 10 to 100 .mu.m from the viewpoint of a
working property.
[0053] The photosensitive resin composition film of the present
invention may have a cover film on the photosensitive resin
composition film for protecting the surface. Examples of the cover
film include a polyethylene film, a polypropylene (PP) film and a
polyester film. The cover film has preferably a low adhesion force
with a photosensitive adhesive film.
[0054] Examples of the method for forming the laminate of the
present invention include a method in which the photosensitive
resin composition of the present invention is applied onto a film
of a support, and dried, and a cover film is laminated to the
surface of the photosensitive resin composition film.
[0055] Examples of the method for applying the photosensitive resin
composition to the support include spin coating using a spinner,
spray coating, roll coating, screen printing, blade coating, die
coating, calender coating, meniscus coating, bar coating, comma
roll coating, gravure coating, and slit die coating. The coating
film thickness varies depending on the coating method, the solid
concentration of the composition, the viscosity and so on, but
normally the film thickness after drying is preferably 0.5 .mu.m to
80 .mu.m inclusive.
[0056] For drying, an oven, a hot plate, an infrared oven or the
like can be used. The drying temperature and the drying time should
be in a range which allows an organic solvent to be volatilized,
and it is preferable to appropriately conditions which ensure that
the photosensitive resin composition film is in an uncured or
semi-cured state. Specifically, drying is preferably carried out at
a temperature in a range of 40.degree. C. to 120.degree. C. for one
minute to several tens of minutes. These temperatures may be
combined to elevate the temperature, and for example, a heat
treatment may be carried out at 70.degree. C., 80.degree. C. and
90.degree. C. for one minute for each temperature.
[0057] An exemplary method for pattern-processing the
photosensitive resin composition of the present invention and the
photosensitive resin composition film using the same, and an
exemplary method for thermocompression to other members will now be
described by showing an example.
[0058] First, a photosensitive resin composition coating is formed
on a substrate using the photosensitive resin composition of the
present invention and the photosensitive resin composition film
using the same. The photosensitive resin composition is applied
onto a substrate, and dried as necessary, whereby a coating can be
formed. Examples of the coating method include spin coating using a
spinner, spray coating, roll coating and screen printing. The
coating film thickness varies depending on the coating method, the
solid concentration of the resin composition, the viscosity and so
on, but normally it is preferable to apply the composition so that
the film thickness after drying is 0.5 .mu.m to 80 .mu.m inclusive.
For drying, an oven, a hot plate, an infrared oven or the like can
be used. The drying temperature and the drying time should be in a
range which allows an organic solvent to be volatilized, and it is
preferable to appropriately set a range which ensures that the
photosensitive resin composition coating is in an uncured or
semi-cured state. Specifically, drying is preferably carried out at
a temperature in a range of 50.degree. C. to 150.degree. C. for one
minute to several hours.
[0059] On the other hand, if the photosensitive resin composition
film has a cover film, the cover film is peeled off, and the
photosensitive resin composition film and the substrate are
laminated together by thermocompression such that the former and
the latter are opposite to each other. Thermocompression can be
performed by a heat press process, a heat lamination process, a
heat vacuum lamination process or the like. The laminating
temperature is preferably not lower than 40.degree. C. from the
viewpoint of conformability to raised and recessed portions of the
substrate. The laminating temperature is preferably not higher than
150.degree. C. for preventing deterioration of the pattern
resolution due to curing of the photosensitive resin composition
film at the time of laminating.
[0060] Examples of the substrate include, but are not limited to, a
silicon wafer, a ceramic, gallium arsenide, an organic circuit
substrate, an inorganic circuit substrate, and these substrates on
which circuit constituent materials are placed. Examples of the
organic circuit substrate include glass base copper-clad laminates
such as a glass fabric/epoxy copper-clad laminate, composite
copper-clad laminates such as a glass nonwoven fabric/epoxy
copper-clad laminate, heat-resistant/thermoplastic substrates such
as a polyether imide resin substrate, a polyether ketone resin
substrate and a polysulfone-based resin substrate, and flexible
substrates such as a polyester copper-clad film substrate and a
polyimide copper-clad film substrate. Examples of the inorganic
circuit substrate include ceramic substrates such as an aluminum
substrate, an aluminum nitride substrate and a silicon carbide
substrate, and metal-based substrates such as an aluminum base
substrate and an iron base substrate. Examples of the circuit
constituent material include conductors containing metals such as
silver, gold, copper and aluminum, resistors containing an
inorganic oxide and so on, low dielectric materials containing a
glass-based material and/or a resin and so on, high dielectric
materials containing a resin, inorganic particles having a high
dielectric constant, and so on, and insulators containing a
glass-based material and so on.
[0061] Next, the photosensitive resin composition coating formed by
the above-mentioned method is irradiated with exposure light
through a mask having a predetermined pattern to perform exposure.
As an exposure light source, an i-line (365 nm), an h-line (405 nm)
and a g-line (436 nm) of a mercury lamp are preferably used. The
photosensitive resin composition film may be exposed without
peeling off the support from the photosensitive resin composition
film if the support is a material that is transparent to these
rays. As exposure equipment, a stepper type exposure system or a
mask aligner, a mirror projection type exposure system or the like
can be used.
[0062] For forming a pattern, exposed areas are removed with a
developer after exposure. The developer is preferably an aqueous
solution of tetramethyl ammonium hydroxide, or an aqueous solution
of an alkaline compound such as diethanolamine,
diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium
carbonate, potassium carbonate, triethylamine, diethylamine,
methylamine, dimethylamine, dimethylaminoethyl acetate,
dimethylaminoethanol, dimethylaminoethylmethacrylate,
cyclohexylamine, ethylenediamine or hexamethylenediamine. In some
cases, one of polar solvents such as N-methyl-2-pyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide,
.gamma.-butyrolactone and dimethylacrylamide, alcohols such as
methanol, ethanol and isopropanol, esters such as ethyl lactate and
propylene glycol monomethyl ether acetate, and ketones such as
cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl
ketone, or a combination of several kinds thereof may be included
in the aforementioned aqueous alkali solution.
[0063] Development can be performed by a method in which the
developer is sprayed to the surface of the coating, a method in
which the developer is deposited on the surface of the coating, a
method in which the film is immersed in the developer, a method in
which the film is immersed and subjected to ultrasonication, or the
like. Development conditions such as the development time, the
development step and the temperature of the developer should be
conditions which ensure that exposed areas can be removed to form a
pattern.
[0064] The developer is preferably rinsed with water after
development. The developer may be rinsed with water plus an alcohol
such as ethanol or isopropyl alcohol, an ester such as ethyl
lactate or propylene glycol monomethyl ether acetate, or the
like.
[0065] A baking treatment may be carried out as necessary before
development. Consequently, the resolution of the pattern after
development is improved, or the allowable range of development
conditions is increased in some cases. The temperature of the
baking treatment is preferably in a range of 50 to 180.degree. C.,
more preferably in a range of 60 to 120.degree. C. in particular.
The time is preferably 5 seconds to several hours.
[0066] After formation of a pattern, a quinonediazide compound
remains in the photosensitive resin composition coating. Therefore,
the compound may be thermally decomposed to produce nitrogen at the
time of thermodecompression or curing. For prevention thereof, the
entire surface of the photosensitive resin composition coating
after formation of a pattern is preferably irradiated with the
above-mentioned exposure light to decompose the quinonediazide
compound beforehand. This process is referred to as bleaching
exposure.
[0067] After formation of a pattern or bleaching exposure, the
photosensitive resin composition coating is dried by heating at a
temperature in a range of 60 to 200.degree. C. for reducing a
solvent, a volatile component, water, nitrogen and so on that
remain in the photosensitive resin composition coating. The time is
preferably one minute to several hours.
[0068] The substrate provided with the photosensitive resin
composition coating, on which a pattern is formed, is thermally
compressed on a substrate or any other member to be temporarily
fixed. The thermocompression temperature is preferably in a
temperature range of 100 to 150.degree. C. The pressure during
thermocompression is preferably in a range of 0.01 to 10 MPa. The
time is preferably one second to several minutes. Thermocompression
may be performed under normal pressure, or may be performed in
vacuum for prevention of trapping of air bubbles and so on.
[0069] After thermocompression, the photosensitive resin
composition coating is formed into a cured film by heating at a
temperature of 120.degree. C. to 400.degree. C. For this heating
treatment, a temperature is selected and elevated stepwise, or a
certain temperature range is selected, and the temperature is
continuously elevated for 5 minutes to 5 hours. As one example, the
heat treatment is carried out at 130.degree. C. and 200.degree. C.
for 30 minutes for each temperature. Alternatively, mention is made
of a method in which the temperature is linearly elevated from room
temperature to 250.degree. C. for 2 hours. At this time, the
heating temperature is preferably 150.degree. C. to 300.degree. C.
inclusive, and further preferably 180.degree. C. to 250.degree. C.
inclusive. The heating treatment may be performed under normal
pressure, or may be performed in vacuum.
[0070] The adhesion strength of the bonded object after curing is
preferably not less than 30 MPa from the viewpoint of adhesion
reliability. More preferable is no less than 45 MPa.
[0071] The film thickness of the cured film can be arbitrarily set,
but is preferably 0.5 .mu.m to 80 .mu.M inclusive.
[0072] A semiconductor device having a photosensitive resin
composition cured film will now be described as an application of
the photosensitive resin composition and the photosensitive resin
composition film of the present invention. In recent years,
semiconductor devices of various structures have been proposed, and
the application of the photosensitive resin composition of the
present invention is not limited to those described below.
[0073] The photosensitive resin composition and the photosensitive
resin composition film of the present invention can be suitably
used as an adhesive for a semiconductor for bonding, fixing and
sealing a semiconductor element, a semiconductor device, a circuit
substrate and a metal wiring material. The photosensitive resin
composition and the photosensitive resin composition film of the
present invention can also be used as an insulating film for a
semiconductor element, a semiconductor device, a circuit substrate
and so on. The semiconductor device in the present invention refers
to not just a product prepared by bonding a semiconductor element
to a substrate, and a product prepared by bonding semiconductor
elements or bonding substrates, but also refers to all devices that
can function by utilizing the properties of semiconductor elements,
and electro-optic devices, semiconductor circuit substrates and
electronic components including them are all encompassed in the
semiconductor device.
[0074] One example of the method for producing a semiconductor
device using the photosensitive resin composition and the
photosensitive resin composition film of the present invention is
as follows. A first circuit member having a first jointing terminal
and a second circuit member having a second jointing terminal are
placed such that the first jointing terminal and the second
jointing terminal are opposite to each other. Next, the
photosensitive resin composition film of the present invention is
interposed between the first jointing terminal and the second
jointing terminal placed opposite to each other to form a
photosensitive resin composition coating. Alternatively, a varnish
of the photosensitive resin composition is applied to any one or
both of the surface of the first jointing terminal and the second
jointing terminal, and dried to thereby form a photosensitive resin
composition coating. Next, the photosensitive resin composition
coating is patterned to open an area where conduction should be
provided between the first jointing terminal and the second
jointing terminal. Thereafter, the first circuit member and the
second circuit member are heated and compressed to electrically
connect these circuit members.
[0075] Electrical connection may be performed after first forming
the photosensitive resin composition coating on the surface of only
any one of the circuit members at the jointing terminal side, or
may be performed after forming the photosensitive resin composition
coating on the surfaces of both the first and second circuit
members at the jointing terminal side. A through electrode may be
formed on the first circuit member and/or the second circuit
member, and the jointing terminal may be formed on one surface
and/or both the surfaces of the member. As such as circuit member,
a chip component such a semiconductor chip provided with bumps such
as a plated bump and a stud bump, a chip Resistor or a chip
condenser, a semiconductor chip having a TSV (through silicon via)
electrode, or a silicon interposer, a substrate such as a glass
epoxy circuit substrate or a film circuit substrate, or the like is
used. A semiconductor device with circuit members laminated
three-dimensionally is obtained by repeatedly performing such
connection as described above using circuit members having jointing
terminals on both the surfaces.
[0076] In the above-mentioned method for producing a semiconductor
device, by using the photosensitive resin composition and the
photosensitive resin composition film of the present invention,
there can be obtained a semiconductor device in which the edge of
an adhesive after curing is located at the inner side as compared
to the edge of a circuit member, i.e. a semiconductor device in
which occurrence of protrusion of an adhesive (fillet) to the outer
periphery of circuit members is suppressed after a first circuit
member and a second circuit member are heated and compressed. By
suppressing occurrence of the fillet, the mounting area of the
semiconductor device can be reduced, thus helping make the
semiconductor device lighter, thinner and more compact. Even if the
photosensitive resin composition of the present invention is not
used, occurrence of the fillet can be suppressed as described above
by ensuring that a resin composition coating is not formed at the
peripheral part of the circuit member beforehand. In this method,
however, alignment is difficult, and further it is very difficult
to form a resin composition coating at a specific location when the
composition is processed into a sheet of wafer. In contrast, in the
method which uses the photosensitive resin composition and the
photosensitive resin composition film of the present invention, a
semiconductor device in which occurrence of the fillet is
suppressed can be easily obtained by removing a photosensitive
resin composition coating at the peripheral part of the circuit
member by patterning.
[0077] One example of the method for producing a semiconductor
device in which occurrence of the fillet is suppressed is as
follows. A photosensitive resin composition coating is formed
between a first circuit member and a second circuit member in the
same manner as in the above-mentioned method for producing a
semiconductor device. Next, the photosensitive resin composition
coating at the peripheral part of the first circuit member and/or
the second circuit member is removed by patterning the
photosensitive resin composition coating. Thereafter, the first
circuit member and the second circuit member are heated and
compressed to bond these circuit members. As a result, there is
obtained a semiconductor device in which a cured product of the
photosensitive resin composition coating does not protrude from the
first circuit member and the second circuit member.
[0078] As another application, on a silicon wafer provided with a
CCD or CMOS image sensor consisting of a photodiode or a color
filter and a micro lens array, a photosensitive resin composition
film is attached, or a varnish of a photosensitive resin
composition is applied and dried to thereby form a photosensitive
resin composition coating. The photosensitive resin composition
coating is patterned, and then a glass substrate is laminated on a
left pattern as a support substrate, and thermally compressed. The
laminate is heated to cure the photosensitive resin composition
coating. In this way, there is obtained an image sensor having a
hollow structure, wherein a semiconductor element and a glass
substrate are bonded with a cured product of the patterned
photosensitive resin composition coating as a barrier wall.
EXAMPLES
[0079] A method for preparing a photosensitive resin composition of
the present invention and a method for producing a photosensitive
resin composition sheet, and a method for evaluating the properties
thereof and the results will be described more specifically below,
but the present invention is not limited thereto.
<Molecular Weight of Synthesized Polyimide>
[0080] A polyimide was dissolved in NMP to prepare a solution
having a solid concentration of 0.1% by weight, and a weight
average molecular weight was calculated in terms of polystyrene by
a GPC apparatus Waters 2690 (manufactured by Waters Co., Ltd.)
having a configuration shown below. For GPC measurement conditions,
the mobile layer was NMP with LiCl and phosphoric acid each
dissolved therein at a concentration of 0.05 mol/L, and the
development rate was 0.4 ml/minute. The column was warmed to
40.degree. C. using a column oven.
Detector: Waters 996
[0081] System controller: Waters 2690
Column: TOSOH TSK-GEL .alpha.-4000
Column: TOSOH TSK-GEL .alpha.-2500
<Imidization Ratio of Synthesized Polyimide>
[0082] First, the infrared spectrum of a polyimide was measured,
and the presence of absorption peaks (around 1780 cm.sup.-1 and
around 1377 cm.sup.-1) originating from an imide structure in the
polyimide was confirmed. Next, the polyimide was subjected to a
heat treatment at 350.degree. C. for an hour, the infrared spectrum
is then measured again, and peak intensities around 1377 cm.sup.-1
before and after the heat treatment were compared. The imidization
ratio of the polyimide before the heat treatment was determined
with the imidization ratio of the polyimide after the heat
treatment set to 100%.
<Spin Coating of Photosensitive Resin Composition>
[0083] A photosensitive resin composition prepared in each of
Examples and Comparative Examples was applied by spin coating onto
a silicon wafer using a spin coater. The rotation time was 10
seconds, and the number of rotations was adjusted to about 500 to
700 rpm so that the film thickness after drying was about 25 .mu.m.
The photosensitive resin composition was dried for 3 minutes on a
hot plate at 100.degree. C. after being applied.
<Lamination of Photosensitive Resin Composition Film>
[0084] A cover film of a photosensitive resin composition film
prepared in each of Examples and Comparative Examples was peeled
off, the peeled surface was laminated onto a silicon wafer under
conditions of stage temperature: 80.degree. C.; roll temperature:
80.degree. C.; degree of vacuum: 150 Pa; attaching rate: 5
mm/second; and attaching pressure: 0.2 Mpa using a lamination
apparatus (VTM-200M manufactured by Takatori Corporation), and a
support film was peeled off.
<Evaluation of Resolution of Photosensitive Resin
Composition>
[0085] A silicon wafer after spin coating or lamination was
pattern-exposed using a mask having a pattern of L/S=70/70, 60/60,
50/50, 40/40, 30/30, 25/25 and 20/20 .mu.m. The exposure gap
between the mask and the photosensitive resin composition film was
100 .mu.m, and L39 filter transmitted light from an ultra-high
pressure mercury lamp was applied in an amount of 400 mJ/cm.sup.2
(photometric value in an h-line). After pattern exposure, exposed
areas were removed using a 2.38% aqueous solution of
tetramethylammonium hydroxide in dip development, and rinsing was
carried out with water. The development time was 1.5 times as long
as the time taken for exposed areas to be fully dissolved. The
obtained pattern was observed with an optical microscope, and a
minimum size with defects such as clogging being absent in lines of
the pattern was evaluated as a resolution.
<Evaluation of Heat Resistance>
[0086] A photosensitive resin composition laminated or applied by
spin coating onto a silicon wafer was exposed in an exposure amount
of 1000 mJ/cm.sup.2 (photometric value in an i-line) using an
ultra-high pressure mercury lamp in the manner described above, and
then heat-treated under an atmosphere of N.sub.2 at 200.degree. C.
for 60 minutes in an inert oven (INL-60 manufactured by Koyo Thermo
Systems Co., Ltd.) to obtain a cured film. The obtained cured film
on the silicon wafer was immersed in 47% hydrofluoric acid at room
temperature for 7 minutes, and then washed with tap water, and the
cured film was peeled off from the silicon wafer. For the peeled
cured film, a thermal weight loss was measured under a condition of
temperature elevation rate: 10.degree. C. under a nitrogen
atmosphere using an apparatus for thermogravimetry (TG/DTA 6200
manufactured by SII NanoTechnology Inc.), and a temperature at
which the weight loss was 1% with respect to a weight at the start
of measurement was designated as an indicator of the heat
resistance.
<Evaluation of Adhesion Strength>
[0087] A photosensitive resin composition laminated or applied by
spin coating onto a silicon wafer was exposed in an exposure amount
of 400 mJ/cm.sup.2 (photometric value in an h-line) in the manner
as described above. The silicon wafer after exposure was cut into
50.times.50 mm, placed on a hot plate at 150.degree. C. with the
photosensitive resin composition film at the upper side, and
preliminarily heated for one minute, and a silicon chip (2.times.2
mm, thickness: 525 .mu.m) was then thermally compressed at a
pressure of 0.2 MPa for 30 seconds to be temporarily fixed.
Thereafter, heat curing was performed at 250.degree. C. for 60
minutes using an inert oven under a nitrogen atmosphere to obtain a
sample with a silicon chip bonded to a silicon wafer with the
photosensitive resin composition interposed therebetween. The shear
strength of the silicon chip of the sample was measured under the
following conditions, and designated as an adhesion strength.
Apparatus: Die shear Tester Series 4000 manufactured by Dage
Corporation Measurement temperature: 30.degree. C. Sample size: 2
mm.times.2 mm Test speed: 200 .mu.m/s Test height: 300 .mu.M
<Evaluation of Stress>
[0088] A measurement was made in the following procedure using a
stress measurement apparatus FLX-2908 manufactured by KLA-Tencor
Corporation. First, a warp of a 6-inch silicon wafer was measured
by a stress measurement apparatus and to this wafer, the
photosensitive resin composition film was laminated or the
photosensitive resin composition was applied by spin coating. This
silicon wafer was exposed in an exposure amount of 1000 mJ/cm.sup.2
(photometric value in an i-line) using an ultra-high pressure
mercury lamp, and then heat-treated under an atmosphere of N.sub.2
at 200.degree. C. for 60 minutes in an inert oven (INL-60
manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured
film. A warp of the substrate after curing was measured by the
stress measurement apparatus again, and a stress at room
temperature was calculated from warps of the wafer before and after
formation of the cured film.
[0089] A polyimide and a quinolinediazide compound used in each of
Examples and Comparative Examples were synthesized by the following
method.
Synthesis Example 1
[0090] To 100 g of N-methyl-2-pyrrolidone (NMP) were dissolved 16.
41 g (0.082 mol) of 4,4'-diaminodiphenyl ether (4,4'-DAE), 1.24 g
(0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA)
and 2.73 g (0.025 mol) of 3-aminophenol (MAP) as an end capping
agent under a dry nitrogen stream. Thereto was added 31.02 g (0.1
mol) of 4,4'-oxydiphthalic dianhydride (ODPA) together with 30 g of
NMP, and the mixture was stirred at 20.degree. C. for an hour, and
then stirred at 50.degree. C. for 4 hours. Thereafter, the mixture
was stirred at 180.degree. C. for 5 hours to obtain a resin
solution. Next, the resin solution was poured in 3 L of water to
collect white precipitates. The precipitates were collected by
filtration, washed with water three times, and then dried in a
vacuum dryer at 80.degree. C. for 5 hours to obtain polyimide A.
The imidization ratio of the obtained resin powder was 95%.
Synthesis Example 2
[0091] To 100 g of NMP were dissolved 30.95 g (0.0845 mol) of
2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 1.24
g (0.005 mol) of SiDA under a dry nitrogen stream. Thereto was
added 31.02 g (0.1 mol) of ODPA together with 30 g of NMP, and the
mixture was stirred at 20.degree. C. for an hour, and then stirred
at 50.degree. C. for 4 hours. Thereto was added 2.5 g (0.02 mol) of
MAP, and the mixture was stirred at 50.degree. C. for 2 hours, and
then stirred at 180.degree. C. for 5 hours to obtain a resin
solution. Next, the resin solution was poured in 3 L of water to
collect white precipitates. The precipitates were collected by
filtration, washed with water three times, and then dried in a
vacuum dryer at 80.degree. C. for 5 hours to obtain polyimide B.
The imidization ratio of the obtained resin powder was 94%.
Synthesis Example 3
[0092] To 100 g of NMP were dissolved 30.03 g (0.082 mol) of BAHF,
1.24 g (0.005 mol) of SiDA and 3.13 g (0.025 mol) of
4-aminothiophenol as an end capping agent under a dry nitrogen
stream. Thereto was added 29.42 g (0.1 mol) of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) together with
30 g of NMP, and the mixture was stirred at 20.degree. C. for an
hour, and then stirred at 50.degree. C. for 4 hours. Thereafter,
the mixture was stirred at 180.degree. C. for 5 hours to obtain a
resin solution. Next, the resin solution was poured in 3 L of water
to collect white precipitates. The precipitates were collected by
filtration, washed with water three times, and then dried in a
vacuum dryer at 80.degree. C. for 5 hours to obtain polyimide C.
The imidization ratio of the obtained resin powder was 94%.
Synthesis Example 4
[0093] To 100 g of NMP were dissolved 30.03 g (0.082 mol) of BAHF,
1.24 g (0.005 mol) of SiDA and 4.1 g (0.025 mol) of
3-hydroxyphthalic anhydride as an end capping agent under a dry
nitrogen stream. Thereto was added 31.02 g (0.1 mol) of ODPA
together with 30 g of NMP, and the mixture was stirred at
20.degree. C. for an hour, and then stirred at 50.degree. C. for 4
hours. Thereafter, the mixture was stirred at 180.degree. C. for 5
hours. After completion of stirring, the solution was poured in 3 L
of water to obtain white precipitates. The precipitates were
collected by filtration, washed with water three times, and then
dried in a vacuum dryer at 80.degree. C. for 5 hours to obtain
polyimide D. The imidization ratio of the obtained polymer powder
was 96%.
Synthesis Example 5
[0094] To 80 g of NMP were dissolved 17.60 g (0.088 mol) of
4,4-DAE, 1.24 g (0.005 mol) of SiDA and 1.64 g (0.015 mol) of MAP
as an end capping agent. Thereto was added 31.02 g (0.1 mol) of
ODPA together with 20 g of NMP, and the mixture was stirred at
20.degree. C. for an hour, and then stirred at 50.degree. C. for 4
hours. Thereafter, 15 g of xylene was added, and the mixture was
stirred at 180.degree. C. for 5 hours while water was boiled with
xylene. After completion of stirring, the solution was poured in 3
L of water to obtain white precipitates. The precipitates were
collected by filtration, washed with water three times, and then
dried in a vacuum dryer at 80.degree. C. for 20 hours to obtain
polyimide E. The imidization ratio of the obtained polymer powder
was
Synthesis Example 6
[0095] To 120 g of NMP were dissolved 16.40 g (0.082 mol) of
4'4-DAE, 1.24 g (0.005 mol) of SiDA and 1.64 g (0.025 mol) of MAP
as an end capping agent under a dry nitrogen stream. Thereto was
added 31.02 g (0.1 mol) of ODPA together with 30 g of NMP, and the
mixture was stirred at 20.degree. C. for an hour, and then stirred
at 50.degree. C. for 4 hours. Thereafter, the mixture was stirred
at 180.degree. C. for 5 hours to obtain a resin solution. Next, the
resin solution was poured in 3 L of water to collect white
precipitates. The precipitates were collected by filtration, washed
with water three times, and then dried in a vacuum dryer at
80.degree. C. for 5 hours to obtain polyimide F. The imidization
ratio of the obtained resin powder was 95%.
Synthesis Example 7
[0096] To 100 g of N-methyl-2-pyrrolidone (NMP) were dissolved 16.
41 g (0.082 mol) of 4,4'-diaminodiphenyl ether (4,4'-DAE), 1.24 g
(0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (SiDA)
and 2.73 g (0.025 mol) of 3-aminophenol (MAP) as an end capping
agent under a dry nitrogen stream. Thereto was added 31.02 g (0.1
mol) of 4,4'-oxydiphthalic dianhydride (ODPA) together with 30 g of
NMP, and the mixture was stirred at 20.degree. C. for an hour, and
then stirred at 50.degree. C. for 4 hours. Thereafter, the mixture
was stirred at 180.degree. C. for 2.5 hours to obtain a resin
solution. Next, the resin solution was poured in 3 L of water to
collect white precipitates. The precipitates were collected by
filtration, washed with water three times, and then dried in a
vacuum dryer at 80.degree. C. for 3 hours to obtain polyimide G.
The imidization ratio of the obtained resin powder was 83%.
Synthesis Example 8
[0097] To 80 g of NMP were dissolved 11.41 g (0.057 mol) of
4,4'-DAE, 1.24 g (0.005 mol) of SiDA and 6.98 g (0.075 mol) of
aniline as an end capping agent. Thereto was added 31.02 g (0.1
mol) of ODPA together with 20 g of NMP, and the mixture was stirred
at 20.degree. C. for an hour, and then stirred at 50.degree. C. for
4 hours. Thereafter, the mixture was stirred at 180.degree. C. for
5 hours to obtain a resin solution. Next, the resin solution was
poured in 3 L of water to collect white precipitates. The
precipitates were collected by filtration, washed with water three
times, and then dried in a vacuum dryer at 80.degree. C. for 5
hours to obtain polyimide H. The imidization ratio of the obtained
resin powder was 95%.
Synthesis Example 9
[0098] To 450 g of 1,4-dioxane were dissolved 21.22 g (0.05 mol) of
TrisP-PA (product name; manufactured by Honshu Chemical Industry
Co., Ltd.) and 26.8 g (0.1 mol) of 5-naphthoquinonediazidesulfonic
acid chloride (NAC-5 manufactured by Toyo Gosei CO. Ltd.) under a
dry nitrogen stream, and the solution was adjusted to room
temperature. Thereto was added dropwise 12.65 g of triethylamine
mixed with 50 g of 1,4-dioxane while ensuring that the temperature
in the system was not 35.degree. C. or higher. Thereafter, the
mixture was stirred at 40.degree. C. for 2 hours. A triethylamine
salt was filtered, and the filtrate was poured in water.
Thereafter, deposited precipitates were collected by filtration,
and further washed with 1 L of 1% aqueous hydrochloric acid.
Thereafter, the precipitates were further washed with 2 L of water
twice. The precipitates were dried in a vacuum dryer to obtain
quinonediazide compound A represented by the following formula.
##STR00009##
Synthesis Example 10
[0099] To 450 g of 1,4-dioxane were dissolved 12.25 g (0.04 mol) of
Phcc-AP (product name; manufactured by Honshu Chemical Industry
Co., Ltd.) and 26.8 g (0.1 mol) of 5-naphthoquinonediazidesulfonic
acid chloride (NAC-5 manufactured by Toyo Gosei CO. Ltd.) under a
dry nitrogen stream, and the solution was adjusted to room
temperature. Thereto was added dropwise 12.65 g of triethylamine
mixed with 50 g of 1,4-dioxane while ensuring that the temperature
in the system was not 35.degree. C. or higher. Thereafter, the
mixture was stirred at 40.degree. C. for 2 hours. A triethylamine
salt was filtered, and the filtrate was poured in water.
Thereafter, deposited precipitates were collected by filtration,
and further washed with 1 L of 1% aqueous hydrochloric acid.
Thereafter, the precipitates were further washed with 2 L of water
twice. The precipitates were dried in a vacuum dryer to obtain
quinonediazide compound B represented by the following formula.
##STR00010##
Synthesis Example 11
[0100] To 450 g of 1,4-dioxane were dissolved 12.78 g (0.056 mol)
of bisphenol A and 26.8 g (0.1 mol) of
5-naphthoquinonediazidesulfonic acid chloride (NAC-5 manufactured
by Toyo Gosei CO. Ltd.) under a dry nitrogen stream, and the
solution was adjusted to room temperature. Thereto was added
dropwise 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane
while ensuring that the temperature in the system was not
35.degree. C. or higher. Thereafter, the mixture was stirred at
40.degree. C. for 2 hours. A triethylamine salt was filtered, and
the filtrate was poured in water. Thereafter, deposited
precipitates were collected by filtration, and further washed with
1 L of 1% aqueous hydrochloric acid. Thereafter, the precipitates
were further washed with 2 L of water twice. The precipitates were
dried in a vacuum dryer to obtain quinonediazide compound C
represented by the following formula.
##STR00011##
Synthesis Example 12
[0101] To a 500 ml flask were placed 5 g of
2,2'-azobis(isobutyronitrile), 5 g of t-dodecanethiol and 150 g of
propylene glycol monomethyl ether acetate (hereinafter abbreviated
as PGMEA). Thereafter, 30 g of methacrylic acid, 35 g of benzyl
methacrylate and 35 g of octahydro-1H-4,7-methanoindene-5-yl
methacrylate were placed, and the mixture was stirred at room
temperature for some time, air in the flask was replaced by
nitrogen, and the mixture was then stirred at 70.degree. C. for 5
hours. Next, to the resulting solution were added 15 g of glycidyl
methacrylate, 1 g of dimethylbenzylamine and 0.2 g of
p-methoxyphenol, and the mixture was stirred at 90.degree. C. for 4
hours to obtain an acrylic resin solution. The solid concentration
of the obtained acrylic resin solution was 43% by weight, and the
obtained resin had a weight average molecular weight (Mw) of 10600
and an acid value of 118 mg KOH/g.
Example 1
[0102] (a) 10 g of polyimide A obtained in Synthesis example 1, (b)
2.0 g of OXT-191 (product name; manufactured by Toagosei Co., Ltd.)
and (c) 2.0 g of quinonediazide compound A were dissolved in a
solvent that was diacetone alcohol/ethyl lactate in a ratio of
40/60. The added amount of the solvent was adjusted so that the
solid concentration was 45% by weight with components other than
the solvent being considered as solids. Thereafter, the solution
was filtered under pressure using a filter with a retention
particle diameter of 2 .mu.m to obtain a photosensitive resin
composition (Table 1).
[0103] The obtained photosensitive adhesive was applied onto a PET
film having a thickness of 38 .mu.m using a comma roll coater, and
dried at 75.degree. C. for 6 minutes, and a PP film having a
thickness of 10 .mu.m was then laminated as a cover film to obtain
a photosensitive resin composition film. Coating was performed so
that the film thickness of the photosensitive resin composition
film was about 25 .mu.m. The obtained photosensitive adhesive film
was used to evaluate the resolution, the heat resistance, the
adhesion strength and the stress in the manner described
previously.
Examples 2 to 12
[0104] A photosensitive resin composition film was prepared in the
mixing ratio shown in Table 1 in the same manner as in Example 1,
and the resolution, the heat resistance, the adhesion strength and
the stress were evaluated in the manner described previously.
Example 13
[0105] The photosensitive resin composition of Example 1 was
applied by spin coating to a silicon wafer by the method described
above to form a coated film. The obtained product was used to
evaluate the resolution, the heat resistance, the adhesion strength
and the stress.
Example 14
[0106] The photosensitive resin composition of Example 3 was
applied by spin coating to a silicon wafer by the method described
above to form a coated film. The obtained product was used to
evaluate the resolution, the heat resistance, the adhesion strength
and the stress.
Comparative Examples 1 to 3
[0107] A photosensitive resin composition film was prepared in the
mixing ratio shown in Table 2 in the same manner as in Example 1,
and the resolution, the heat resistance, the adhesion strength and
the stress were evaluated in the manner described previously.
Reference Example 1
[0108] A photosensitive resin composition was prepared in
accordance with the composition described in Table 2, and an
attempt was made to form a photosensitive resin composition film in
the same manner as in Example 1, but cracks occurred in a film
state because the film was fragile, so that the resolution, the
adhesion strength and the stress could not be evaluated. For the
film after curing, only the heat resistance was evaluated.
Reference Example 2
[0109] The photosensitive resin composition of Reference Example 1
was applied by spin coating to a silicon wafer by the method
described above to form a coated film. The obtained product was
used to evaluate the resolution, the heat resistance, the adhesion
strength and the stress.
Example 15
[0110] The photosensitive resin composition film obtained in
Example 2 was laminated onto a copper comb Electrode of L/S=10
.mu.m/10 .mu.m by vacuum lamination. Thereafter, the coating of the
electrode part was wiped off with acetone. Next, the laminate was
exposed in an exposure amount of 1000 mJ/cm.sup.2 (photometric
value in an i-line) using an ultra-high pressure mercury lamp, and
then heat-treated under an atmosphere of N.sub.2 at 200.degree. C.
for 60 minutes in an inert oven to prepare a sample for evaluation.
An insulation reliability test of 1000 hours was conducted by
continuously applying a voltage of 50 V to between electrodes of
the obtained sample for evaluation under an atmosphere of
temperature: 85.degree. C. and relative humidity: 85%. The
resistance value was kept at 10.sup.10.OMEGA. up to 1000 hours, and
therefore the sample was considered acceptable for the insulation
reliability. For the copper comb Electrode, such an electrode was
used that on a silicon wafer on which a thermal oxide film having a
thickness of 0.4 .mu.m was formed and a silicon nitride film having
a thickness of 0.8 .mu.M was formed thereon, a chromium ground
electrode having a thickness of 0.08 .mu.m was pattern-formed and a
copper electrode having a thickness of 10 .mu.m was pattern-formed
thereon.
Example 16
[0111] This Example will be described with reference to FIG. 1.
First, a Ni layer (10 nm) as an adhesive layer 101 was formed on a
silicon wafer 100 and an electroless copper plated layer (10 .mu.m)
as a conductor layer 102 was formed thereon by sputtering.
[0112] Thereafter, the photosensitive adhesive varnish obtained in
Example 2 was applied by spin coating onto the substrate using a
spin coater, and dried to form a photosensitive resin composition
coating. Thereafter, a via hole was formed in the photosensitive
resin composition coating by exposure and development, and the
photosensitive resin composition coating was cured by carrying out
a heating treatment in an inert oven to obtain a substrate having a
via hole layer 102 (FIG. 1 (a)).
[0113] Then, the photosensitive resin composition varnish obtained
in Example 2 was applied by spin coating to the substrate using a
spin coater, a pattern (space area) forming a wiring hole layer was
formed by drying, exposure and development, and the wiring hole
layer 103 was cured by carrying out a heating treatment in an inert
oven to obtain a substrate having a via hole/wiring hole (FIG. 1
(b)).
[0114] Then, a Ni layer (thickness: 10 nm) as an adhesive layer was
formed on the substrate by sputtering, and electrolytic copper
plating was performed to fill the via hole and the wiring hole with
copper plating. Thereafter, copper plating of unwanted areas were
removed and the surface of an insulating film was flattened by
chemical mechanical polishing (CMP) to obtain a substrate having a
via layer/wiring layer 104 (FIG. 1 (c)).
[0115] Thereafter, with formation of a via layer/wiring layer by
the above-mentioned method designated as one cycle, the cycle was
repeated three times to prepare a multilayer wiring substrate
having total 8 layers in which 4 via layers and 4 wiring layers
were laminated. As a result of checking presence/absence of defects
such as detachment and cracks of the insulating layer in the
prepared multilayer wiring substrate, these defects were not
observed. As a result of checking conduction between any outermost
wiring layer and the undermost conductor layer in the prepared
multilayer wiring substrate using a tester, it could be found that
conduction was provided between wirings at any location and that no
short circuit occurred between adjacent wirings.
[0116] Compounds (b) used in Examples and Comparative Examples are
as follows.
[0117] jER828: BisA type epoxy compound (manufactured by Mitsubishi
Chemical Corporation)
[0118] OXT-191: Oxetane compound (manufactured by Toagosei Co.,
Ltd.)
##STR00012##
[0119] EP4003S: Propylene oxide-modified BisA type epoxy resin
(manufactured by ADEKA Corporation)
[0120] jER152: Phenol novolac epoxy resin (manufactured by
Mitsubishi Chemical Corporation)
[0121] jER630: Glycidylamine type epoxy resin (manufactured by
Mitsubishi Chemical Corporation)
[0122] NC3000: Biphenyl type epoxy resin (manufactured by Nippon
Kayaku Co., Ltd.)
[0123] "EPICLON (registered trademark)" 850S: BisA type epoxy resin
(manufactured by DIC Corporation)
TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple ple Items 1 2
3 4 5 6 7 8 9 10 Polyimide A B C D E F B B A C Com- Acid ODPA 100
100 -- 100 100 100 100 100 100 -- position anhydride BPDA -- -- 100
-- -- -- -- -- -- 100 of Diamine BAHF -- 84.5 82 82 -- -- 84.5 84.5
-- 82 poly- 4,4'-DAE 82 -- -- -- 88 82 -- -- 82 -- imide SiDA 5 5 5
5 5 5 5 5 5 5 (molar End MAP 25 20 -- -- 15 25 20 20 25 -- ratio)
capping 4-amino- -- -- 25 -- -- -- -- -- -- 25 agent thio- phenol
3- -- -- -- 25 -- -- -- -- -- -- hydroxy- phthalic acid Aniline --
-- -- -- -- -- -- -- -- -- Imidization ratio (%) 95 94 94 96 95 95
94 94 95 94 of polyimide Weight average molecular 19900 25600 21200
22500 56000 19900 25600 25600 19900 21200 weight of polyimide
Photo- Polyimide (a) 100 100 100 100 100 100 100 100 100 100 sensi-
Compound jER828 -- -- -- 20 -- -- -- -- -- -- tive (b) OXT-191 20
-- -- -- -- -- 10 -- 25 -- com- EP4003S -- 30 40 -- -- -- 50 -- --
40 position jER152 -- -- -- -- 40 20 -- -- -- -- Com- iER630 -- 30
-- -- 20 -- -- 30 -- -- position NC3000 -- -- -- 40 -- -- -- -- --
-- (parts EPICLON- -- -- -- -- -- -- -- 30 -- -- by 850 weight)
Quinone- A 20 -- -- -- 40 -- -- -- 7 diazide B -- 10 20 5 -- -- --
30 -- 20 compound C -- -- -- -- -- 20 45 -- -- -- (c) Others
Acrylic -- -- -- -- -- -- -- -- -- 5 resin solution of Synthesis
Example 10 Resolution (.mu.m) 25 30 25 40 25 30 25 25 40 25 Heat
resistance (.degree. C.) 346 351 348 361 340 356 335 349 365 311
Adhesion strength (MPa) 32 48 40 41 49 31 45 51 36 30 Stress (MPa)
26 19 20 20 18 24 17 18 25 29
TABLE-US-00002 TABLE 2 Com- Com- Com- par- par- par- Refer- Refer-
ative ative ative ence ence Exam- Exam- Exam- Exam- Exam- Exam-
Exam- Exam- Exam- ple ple ple ple ple ple ple ple ple Items 11 12
13 14 1 2 3 1 2 Polyimide G C A C H A B A A Com- Acid ODPA 100 --
100 -- 100 100 100 100 100 position anhydride BPDA -- 100 -- 100 --
-- -- -- -- of Diamine BAHF -- 82 -- 82 -- -- 84.5 -- -- poly-
4,4'-DAE 82 -- 82 -- 57 82 -- 82 82 imide SiDA 5 5 5 5 5 5 5 5 5
(molar End MAP 25 -- 25 -- -- 25 20 25 25 ratio) capping 4-amino-
-- 25 -- 25 -- -- -- -- -- agent thio- phenol 3- -- -- -- -- -- --
-- -- -- hydroxy- phthalic acid Aniline -- -- -- -- 75 -- -- -- --
Imidization ratio (%) 83 94 95 94 95 95 94 95 95 of polyimide
Weight average molecular 18700 21200 19900 21200 11000 19900 25600
19900 19900 weight of polyimide Photo- Polyimide (a) 100 100 100
100 100 100 100 100 100 sensi- Com- jER828 -- -- -- -- -- 15 -- --
-- tive pound OXT-191 20 -- 20 -- -- -- -- -- -- com- (b) EP4003S
-- 20 -- 40 10 -- 10 40 40 position jER152 -- -- -- -- -- -- -- --
-- Com- jER630 -- -- -- -- -- -- -- -- -- position NC3000 -- -- --
-- -- -- -- -- -- (parts EPICLON- -- -- -- -- -- -- -- -- -- by 850
weight) Quinone- A 20 -- 20 -- -- 20 -- -- -- diazide B -- 20 -- 20
20 -- 10 20 20 com- C -- -- -- -- -- -- -- -- -- pound (c) Others
Acrylic -- -- -- -- -- -- -- 12 12 resin solution of Synthesis
Example 10 Resolution (.mu.m) 30 40 25 25 70 50 40 Eval- 40 uation
impos- sible Heat resistance (.degree. C.) 308 353 346 348 353 346
350 264 264 Adhesion strength (MPa) 31 34 32 40 14 12 19 Eval- 21
uation impos- sible Stress (MPa) 30 26 25 20 32 31 32 Eval- 25
uation impos- sible
[0124] According to the present invention, there is obtained a
photosensitive resin composition and a photosensitive resin
composition film, each of which is capable of forming a positive
tone pattern by photolithography, has small stress after curing,
and exhibits a high strength of adhesion with a semiconductor
element and a support member.
DESCRIPTION OF REFERENCE SIGNS
[0125] 100 silicon wafer [0126] 101 adhesive layer [0127] 102
conductor layer [0128] 103 via hole layer [0129] 104 wiring hole
layer [0130] 105 via layer/wiring layer
* * * * *